Pesticidal compounds, compositions and methods

ABSTRACT

Novel compounds are described which are substituted benzophenone hydrazones. They have pesticidal activity, especially against insects and acarids, and pesticidal compositions and methods are described. Methods of making the compounds, and novel intermediates, are also described.

This invention relates to compounds having pesticidal activity.

Commercially available insecticidal products generally fall into four main categories, namely chlorinated compounds such as DDT, camphechlor and BHC, organophosphorus compounds such as parathion, carbamates such as carbaryl and, more recently, synthetic pyrethroids such as permethrin.

Resistance to an insecticide often develops after a period of use and there is therefore always a need for new insecticides and particularly for new groups of insecticides.

Many proposals appear in the literature that a group of compounds has pesticidal properties, but often such compounds are found not to be commercially acceptable as pesticides.

We have now found that certain benzophenone hydrazones have insecticidal activity against a wide range of pests.

Certain benzophenone hydrazones are already known. For instance in U.S. Pat. No. 3,732,307 there are described compounds of the formula: ##STR1## wherein X is selected from the group consisting of perfluoroalkyl, perfluoroalkoxy and perfluoroalkylthio containing up to four carbon atoms, and

Y is selected from the group consisting of hydrogen, chlorine, bromine, fluorine, alkyl, alkoxy, alkylthio, perfluoroalkyl, perfluoroalkoxy and perfluoroalkylthio containing up to four carbon atoms.

These compounds are distinguished in that specification from, for example, benzophenone hydrazones described by J. R. DoAmaral et. al., J. Med. Chem. 12,21 (1969) apparently by virtue of, inter alia, having the hydrazone NH₂ unsubstituted in the compounds of U.S. Pat. No. 3,732,307. The compounds of that specification are described primarily as plant growth regulants although it is also mentioned in U.S. Pat. No. 3,732,307 that the compounds have activity against insects.

We have now found that certain hydrazones containing substituents other than those described for X and Y have valuable insecticidal properties.

According to the invention there are provided compounds of formula I ##STR2##

where R^(a) is optionally substituted alkyl or aryl, R^(b) is optionally substituted alkyl, R^(c) is fluorine, p-nitrophenyl, 3,5-di(trifluoromethyl)phenyl or aryloxy, R^(d) is monoalkylamino, n is 1 to 3, p is at least 1, q is at least 1, r is 0 to 2n-1, p+q+r=2n+1, X is halogen other than fluorine, and Z is oxygen or sulphur;

R² and R⁴ may be the same or different and are hydrogen, alkyl, acyl, an ester or thioester group, optionally substituted carbamoyl, optionally substituted alkylsulphonyl, arylsulphonyl, N-substituted iminoalkyl, optionally substituted alkenyl, optionally substituted alkynyl, heteroaryl, substituted alkyl or ##STR3## where R^(a) and Z have the meanings given above; or R² and R⁴ together with the nitrogen to which they are attached form a 5 to 7 membered ring which may optionally contain one or more heteroatoms, or R² and R⁴ together form the group ═CR⁵ R⁶, where R⁵ and R⁶ may be the same or different and are hydrogen, optionally substituted alkyl, optionally substituted cycloalkyl, optionally substituted alkenyl, optionally substituted alkoxy, optionally substituted amino, optionally substituted alkenyloxy, aryloxy or aryl, or R⁵ and R⁶ together with the carbon to which they are attached form a ring which may optionally contain one or more heteroatoms; and

Q is a phenyl group optionally substituted by one or more groups selected from halogen, alkyl, haloalkyl, alkoxy, aryloxy, aryl, aralkyl, alkenyl and cyano, or is hydrogen, optionally substituted alkyl or cycloalkyl

or (b) R is R³ SO₂ O-- where R³ is optionally substituted alkyl, alkenyl, N,N-dialkylamino or phenyl optionally substituted by alkyl or halogen; and

(i) one of R² and R⁴ is optionally substituted alkylsulphonyl, arylsulphonyl, N-substituted iminoalkyl, optionally substituted alkenyl, optionally substituted alkynyl, substituted alkyl, heteroaryl or ##STR4## where R^(a) and Z have the meanings given above; and the other has the meaning given under (a) above for a single group, or R² and R⁴ together form the group ═CR⁵ R⁶, where R⁵ and R⁶ have the meanings given under (a) above, and Q has the definition given in (a) above or

(ii) R² and R⁴ may be the same or different and are hydrogen, alkyl, acyl, an ester or thioester group, optionally substituted carbamoyl, optionally substituted thiocarbamoyl or R² and R⁴ together with the nitrogen to which they are attached form a 5 to 7 membered ring which may optionally contain one or more heteroatoms and

Q is a phenyl group having at least one substituent selected from aryloxy, aralkyl, alkenyl and cyano and optionally one or more substituents selected from halogen, alkyl, haloalkyl and alkoxy, or is hydrogen, optionally substituted alkyl or cycloalkyl.

A preferred group of compounds of the invention are compounds of formula I wherein ##STR5##

where R^(a) is optionally substituted alkyl or aryl, R^(b) is optionally substituted alkyl, R^(c) is fluorine, p-nitrophenyl, 3,5-di(trifluoromethyl)phenyl or aryloxy, R^(d) is monoalkylamine, n is 1 to 3, p is at least 1, q is at least 1, r is 0 to 2n-1, p+q+r=2n+1, X is halogen other than fluorine, R³ is optionally substituted alkyl, alkenyl, N,N-dialkylamine or phenyl optionally substituted by alkyl or halogen, and Z is oxygen or sulphur and

R² and R⁴ together form the group ═CR⁵ R⁶, where R⁵ and R⁶ may be the same or different and are hydrogen, optionally substituted alkyl, optionally substituted cycloalkyl, optionally substituted alkenyl, optionally substituted alkoxy, optionally substituted amino, optionally substituted alkenyloxy, aryloxy or aryl, or R⁵ and R⁶ together with the carbon to which they are attached form a ring which may optionally contain one or more heteroatoms; and

Q is a phenyl group optionally substituted by one or more groups selected from halogen, alkyl, haloalkyl, alkoxy, aryloxy, aryl, aralkyl, alkenyl and cyano, or is hydrogen, optionally substituted alkyl or cycloalkyl.

Any alkyl, alkenyl, alkynyl, alkoxy or alkenyloxy groups are generally C₁₋₄. If they are substituted, suitable substituents include halo, phenyl, phenoxy, cyano, alkylamino and alkoxycarbonyl and for alkyl the substituents may include also alkyl. Preferred substituents for particular groups are given in more detail below.

In the present specification any references to halo or halogen should be construed as a reference to fluorine, chlorine, bromine or iodine, preferably fluorine, chlorine or bromine.

In Formula I, Q is preferably a monosubstituted phenyl group with the substituent preferably in the 4-position and is especially 4-halophenyl, e.g., 4-chlorophenyl. Examples of other substituents include trifluoromethyl, phenyl, phenoxy, vinyl and cyano. When Q is optionally substituted alkyl, this is preferably C₁₋₄ alkyl.

R is preferably methylsulphonyloxy or trifluoromethylsulphonyloxy. When R is a group containing a substituent R^(b) this is preferably C₁₋₄ alkyl e.g. methyl or ethyl.

When R² and R⁴ form the group ═CR⁵ R⁶, R⁵ and R⁶ are preferably hydrogen, C₁₋₄ alkyl or C₁₋₄ alkoxy. Generally one of R⁵ and R⁶ is not hydrogen. Other suitable groups include C₃₋₆ cycloalkyl, which may be substituted e.g. by C₁₋₄ alkyl; aryl, e.g. phenyl, pyridyl and thienyl; and alkenyl, e.g. allyl. Where R⁵ or R⁶ is substituted alkyl, the substituents may be e.g. halo, phenyl, phenoxy, cyano, alkylamino or alkoxycarbonyl. If R⁵ and R⁶ form a ring, this ring is preferably a 4 to 7-membered ring which may be substituted and may be unsaturated. Suitable substituents include C₁₋₄ alkyl, or two substituents may together form a fused second ring. If one of R⁵ and R⁶ is substituted amino this may be for example mono- or dialkylamino or monocycloalkylamino.

If R² and R⁴ do not form this group then R² is preferably hydrogen and R⁴ is preferably other than hydrogen and is usually a carbonyl derivative. When R² or R⁴ are alkyl this may be, e.g. of 1 to 4 carbon atoms and is preferably methyl. When R² or R⁴ is N-substituted iminoalkyl this may be, for example N-aryliminomethyl where aryl may be for example 2,4-dimethylphenyl. If R² or R⁴ form a ring with the nitrogen to which they are attached this may be for example piperidine, pyrrolidine, thiamorpholine, triazole, morpholine and especially 2-oxazolidinone. If R² or R⁴ are an ester or thioester group this is generally of formula R⁸ XCO, where X is oxygen or sulphur, preferably oxygen and R⁸ is an organic radical e.g. alkyl, e.g. of 1 to 12, preferably 1 to 8 carbon atoms, and especially ethyl, these alkyl groups being optionally substituted, (e.g. by C₁₋₄ alkoxy; C.sub. 3-7 cycloalkyl; halogen; cyano; aryl, such as phenyl, substituted phenyl or naphthyl; or aryloxy, such as phenoxy and substituted phenoxy); cycloalkyl; e.g. of 3 to 7 carbon atoms and especially cyclopentyl; alkenyl e.g. of 2 to 12 carbon atoms, which group may optionally be substituted (e.g. by aryl such as phenyl or substituted phenyl); alkynyl e.g. of 2 to 6 carbon atoms; aryl such as optionally substituted phenyl or 2-naphthyl; heteroaryl, such as furyl, thienyl, pyridyl, and heterocyclyl such as morpholinyl, piperidyl and thiamorpholinyl. Where a phenyl group is substituted this may be by a wide number of groups e.g. C₁₋₄ alkyl, C₁₋₄ haloalkyl, nitro, C₁₋₄ alkoxy, C₁₋₄ alkylthio, C₁₋₄ dialkylamino, phenyl or halogen. If R² or R⁴ are acyl this is generally of formula R⁹ CO where R⁹ is R⁸ as defined above or hydrogen.

If R² or R⁴, in Formula I, is a carbamoyl group, the group may be of the formula --CNR¹⁰ R¹¹ where R¹⁰ and R¹¹ are the same or different and are hydrogen, optionally substituted alkyl or optionally substituted phenyl or together with the nitrogen to which they are attached form a 5 or 7 membered ring which may optionally contain one or more heteroatoms. Suitable optionally substituted alkyl or phenyl or heterocyclic groups are listed above in the description of, for instance, R², R⁴ and R⁸.

A particularly valuable group of compounds are these in which R is trifluoromethylsulphonyloxy or methanesulphonyloxy, Q is 4-chlorophenyl and R² and R⁴ form the group ═CR⁵ R⁶ where one of R⁵ and R⁶ is hydrogen or C₁₋₄ alkyl and the other is C₁₋₄ alkoxy. These compounds generally have a broader spectrum of activity than compounds for instance where R² and R⁴ have other meanings. They are also more soluble in common organic solvents thus enabling the formation of more concentrated compositions which is a particularly important commercial and practical consideration. Another valuable group of compounds are those where R and Q are as above and R⁵ and R⁶ are optionally substituted alkyl or cycloalkyl or together form a ring. These latter compounds generally have a higher activity against aphids than compounds where R² and R⁴ have other meanings.

The compounds of the invention are active against a variety of economically important insects that cause serious and widespread damage to crops such as for example, insects of the order Lepidoptera including caterpillars of the diamond back moth (Plutella xylostella), the cabbage white butterfly (Pieris brassicae), the Egyptian cotton leaf worm (Spodoptera littoralis) and Heliothis spp. such as H.armigera, H.viriscens and H.zea. Many of the compounds have also shown activity against other caterpillars such as these of the codling moth (Laspeyresia pomonella). Some of the compounds have shown activity against other pests such as beetles of the order Colcoptera, including the mustard beetle (Phaedon cochleariae), grain weevil (Sitophilus granarius), flour beetle (Tribolium castaneum) and mealworm (Tenebrio molitor); cockroaches of the order Dictyoptera such as Blatella germanica; aphids of the order Hemiptera, including the vetch aphid (Megoura viciae).

Many of the compounds also have activity against a variety of economically important acarid and insect pests of animals, including farm livestock. For example, many compounds have been shown to be active against larvae stages of insects of the order Diptera e.g. sheep blowfly (Lucilia spp.) and mosquitoes e.g. Aedes aegypti. Some of the compounds, especially those in which R⁶ is alkoxy and R⁵ is hydrogen, have shown systemic activity, i.e. the internal tissues of an animal which has been treated with the compound exert an insecticidal effect. This property is important in the treatment of animals such as cattle, which are infested with tissue-dwelling stages of insects e.g. warble fly (Hypoderma spp.). Some of the compounds are also active against lice and keds and acarid parasites, especially ticks, e.g. Boophilus microplus, and mites, e.g. Sarcoptes spp.

Some of the compounds have also been shown to have nematicidal, fungicidal, herbicidal and plant-growth regulant activity.

The invention also includes an insecticidal composition comprising a compound of formula I and an inert diluent. More than one compound of the invention can be included in the composition, and the diluent can be a solid or liquid, optionally together with a surface active agent, for example a dispersing agent, emulsifying agent or wetting agent.

One or more additional pesticides such as, for example, compounds known to possess acaricidal or insecticidal activity can be added to the composition of the invention to enhance or widen the spectrum of its activity.

Such additional pesticides include, for example, an organophosphorus compound such as tetrachlorvinphos, fenitrothion, demeton-S-methyl, phosalone, dioxathion, chlorfenvinphos, dichlorvos, bromophosethyl, diazinon, dimethoate, methyl parathion, sulprofos, fenthion, trichlorphon, coumaphos, dialifos or chlorpyrifos; a carbamate such as methomyl, carbaryl, pirimicarb or promecarb; a bridged diphenyl compound such as tetradifon, tetrasul or DDT; a chlorinated hydrocarbon such as benzene hexachloride, endosulphan, endrin or toxaphene; an acaricide such as amitraz, chlordimefon, clenpyrin, chlormethiuron or nimidane; a synthetic pyrethroid such as permethrin, fenvalerate, NRDC 161, or cypermethrin; or a tin pesticide such as cyhexatin or fenbutatin oxide.

The composition of the invention can take any of the forms known for the formulation of insecticidal compounds; for example, it can be in the form of a solution, an aqueous dispersion, an aqueous emulsion, an emulsifiable concentrate, a dispersible powder, a dusting powder or granules. Thus it can be in a suitable form for direct application as an insecticide or as a concentrate requiring dilution with an appropriate quantity of water or other diluent before application.

As a dispersion the composition comprises a compound of the invention dispersed in an aqueous medium. It is often convenient to supply the consumer with a concentrate which when diluted with water forms a dispersion of the desired concentration and can be provided in, for example, any of the following forms. It can be a dispersible solution which comprises a compound of the invention dissolved in a water-miscible solvent with the addition of a dispersing agent, or a dispersible powder comprising a compound of the invention and a dispersing agent. A further alternative comprises a compound of the invention in the form of a finely ground powder in association with a dispersing agent and intimately mixed with water to give a paste or cream which can if desired be added to an emulsion of oil in water to give a dispersion of active ingredient in an aqueous oil emulsion.

An emulsion comprises a compound of the invention dissolved in a water-immiscible solvent which is formed into an emulsion with water in the presence of an emulsifying agent. An emulsion of the desired concentration can be formed from a concentrated stock emulsion that comprises a compound of the invention in combination with an emulsifying agent, water and water-immiscible solvent. Alternatively the consumer can be supplied with an emulsifiable concentrate comprising a solution of a compound of the invention in a water-immiscible solvent containing an emulsifying agent.

A dusting powder comprises a compound of the invention intimately mixed and ground with a solid pulverant diluent, for example, kaolin.

A granular solid comprises a compound of the invention associated with similar diluents to those employed in dusting powders but the mixture is granulated by known methods. Alternatively the active ingredient can be absorbed or adsorbed on a pre-formed granular diluent for example fuller's earth, attapulgite or limestone grit.

The concentration of the active ingredient (when used as the sole active component) in a composition for direct application to the crop by conventional ground methods is preferably within the range of 0.001 to 10 percent by weight of the composition, especially 0.005 to 5 percent by weight, but more concentrated compositions containing up to 20 percent may be desirable in the case of aerial sprays. As a concentrated primary composition the concentration of active ingredients may vary widely and can be, for example, from 5 to 95 percent by weight of the composition.

As previously described the compounds of the invention have exceptional activity as insecticides and accordingly the invention includes a method of combating insects which comprises applying a compound of formula I to the locus of the insects, that is, the insects or their habitat. The compound of the invention can either be applied on its own or more preferably as one of the compositions described above.

Many of the insects which the compounds of the invention are active against, for example those of the order Lepidoptera and Coleoptera, attack plant life and a preferred method of the invention is one of the protecting plants from attack by insects by applying a compound of formula 1 to the locus of the plants. For instance the diamond back moth and cabbage white butterfly attack vegetable crops such as brassicas, and leaf worms are a serious pest on cotton.

Direct treatment by for example spraying or dusting the plants infested with insects is often the preferred method but the active compound can also be applied to the soil in which plants are grown as granules, or as a root drench. In such instances the active compound is absorbed by the roots of the plant and confers protection from the insects. The quantity of active compound applied can vary widely depending on the particular circumstances and usually the amount is in the range of from 0.01 to 20 kilogram per hectare, more especially, from 0.1 to 10 kilogram per hectare.

Also included in the invention is a method of protecting animals from attack by pests which comprises treating the animal with a compound of formula I. Parasites are a frequent source of irritation to animals such as livestock and many can be controlled by external application of a compound of formula I. The method may be by direct application to the animals, or by application to the quarters, e.g. buildings, in which the animals live.

The compounds of the invention can be prepared by a number of processes, as follows:

(1) By reacting a compound of formula II ##STR6## with a compound of formula NH₂ NR² R⁴. When R² and R⁴ are both hydrogen the product can then be acylated with (a) an acyl halide or acid anhydride when R² or R⁴ is to is to be any acyl group, with (b) a chloroformate or chlorothioformate when R² or R⁴ is to be an ester group, with (c) an isocyanate when R² or R⁴ is to be a carbamoyl (d) a sulphonyl halide when R² or R⁴ is to be an alkyl or arylsulphonyl group (e) a formimidate when R² or R⁴ is to be an aryliminomethyl compound or (f) when R² and R⁴ together are to form ═CR⁵ R⁶ with (i) a compound of formula O═CR⁵ R⁶ when R⁵ and R⁶ are both not alkoxy or (ii) a compound of formula (R⁵)₃ R⁶ C when at least R⁵ is alkoxy, or a compound of formula R.sup. 5 R⁶ C(O alkyl)₂ when one of R⁵ and R⁶ is substituted amino.

Compounds in which one of R⁵ or R⁶ alkoxy can be reacted with a substituted amine to form a compound in which one of R⁵ or R⁶ is a substituted amino group.

In this specification it will be appreciated that the term "acylating agent" includes all these types of reagent.

The reaction with the hydrazine or hydrazine derivative is usually carried out at a temperature of from 50° C. to 100° C., in the presence of acetic acid or a salt of an organic base and a strong acid e.g. pyridinium chloride.

The acylation reaction is preferably carried out in the presence of an inert organic liquid as the reaction medium which is also preferably a solvent for the reactants, at a temperature of from 0° C. to 100° C. Advantageously the reaction is effected in the presence of a suitably acid-binding agent, for example a tertiary alkylamine, pyridine or an alkali metal carbonate. When the acylating agent is a halide this is preferably the chlorine,

Some of the compounds of formula II are novel and can be prepared by reacting a compound of formula III ##STR7## in which Y is OH, SH or NH₂ when R is an oxy, thio or substituted amino group, respectively with a compound of formula R^(e) X where R^(e) is R minus the oxy, thio or amino group and X is halogen or, when R is R^(b) COO, X may also be hydroxy.

This step is preferably carried out in the presence of any inert organic solvent and an acid binding agent.

When R is R^(d) SO₂ --, Y can be SO₂ Cl and compound III reacted with R^(d) H to give compound II.

(2) By reacting a compound of formula IV ##STR8## in which R² and R⁴ are not both hydrogen with a compound of formula R^(e) X, where Y, R^(e) and X have the meanings given above. The reaction is preferably carried out at a temperature of 0° to 100° C., usually in the presence of an acid binder.

Compounds of formula IV can, in their turn, be prepared by reacting a suitable hydrazine derivative of the formula NH₂ NR² R⁴ with a compound of formula III above, preferably in the presence of an inert organic solvent and optionally together with acetic acid or a salt of an organic base and a strong acid, e.g. pyridinium chloride.

In many cases one compound of the invention may be converted by a suitable analogy process into a second compound of the invention. For instance, compounds in which one of R⁵ and R⁶ is alkoxy can be reacted with an amino group to convert the alkoxy into a substituted amino group.

The present state of our knowledge indicates that most of the above reactions give rise to product that comprises a mixture of the E and Z-isomers.

It is to be understood that formula I above denoting the compounds of the invention includes both of these isomers. In all cases the pairs of isomers can be separated by conventional methods, such as for example chromatography or fractional recrystallisation, but, as the isomeric mixtures have very valuble insecticidal activity, we generally find that there is no advantage in separating the isomers. The activity of the isomers of any one compound may differ and in some cases the activity of one isomer may be negligible; pure isomers lacking insecticidal activity form no part of the present invention.

It will be appreciated that particularly when treating animal pests the products can be administered in a substantial release formulation. Thus the compound may be incorporated in a suitable polymer which may be attached to the animal in the form of an ear tag, collar, leg band etc., or it may be administered as a bolus or implant.

If desired animals may be treated by injection, oral drench or with a pour-on formulation.

The invention is illustrated in the following Examples. The structures of compounds were confirmed by elementary and other appropriate analyses.

EXAMPLES 1-42

Phenol is reacted with p-chlorobenzoyl chloride in a Friedel-Crafts reaction in the presence of aluminium chloride to give 4-chloro-4'-hydroxybenzophenone, m.p. 179°-181° C. (A). To a solution of this (5 g.) in pyridine (6 ml.) was added methanesulphonyl chloride (2.5 g.), at room temperature. The reactants were heated on a steam bath for 11/2 hours and the liquid reaction product poured into dilute hydrochloric acid to give a solid which was filtered and air-dried. This solid was recrystallised from industrial methylated spirits to give 4-chloro-4'-methylsulphonyloxybenzophenone, m.p. 120°-121° C. (B). To a solution of this (9.35 g.) in ethanol (200 ml.) was added hydrazine hydrate (8 ml.) followed by glacial acetic acid (1.5 ml.). The mixture was heated under reflux with stirring for 17 hours. The solvent was evaporated under reduced pressure to give an oil which was extracted with chloroform. The extract was washed with water, aqueous sodium hydroxide and water and then dried over magnesium sulphate. The solvent was evaporated under reduced pressure to give an oil. On standing this crystallised to give 4-chloro-4'-methylsulphonyloxybenzophenone hydrazone, m.p. 70°-110° C. (C). This product (5 g.) was heated under reflux with acetone (25 ml.) for 24 hours. The mixture was then evaporated under reduced pressure to give 4-chloro-4'-methylsulphonyloxybenzophenone isopropylidenehydrazone m.p. 148°-9° C.

In a similar manner using the appropriate starting materials and ketones or aldehydes, the products of Table 1 were obtained. In Example 43, (C) was reacted with 3-amino crotononitrile in acetic acid.

                  TABLE I                                                          ______________________________________                                          ##STR9##                                                                      Ex.                                                                            No.  R.sup.1                                                                               R.sup.16                                                                              R.sup.3                                                                              R.sup.5                                                                             R.sup.6    m.p. (°C.)                     ______________________________________                                         2    Cl     H      Me    Me   Et         110.5-111.5                           3    Cl     H      Me    H    Ph         135-137                               4    Cl     H      Me    Me   CF.sub.3   103-105                               5    Cl     H      CF.sub.3                                                                             Me   Me         Oil                                   6    Cl     H      Me    together are  106.5-115                                                        (CH.sub.2).sub.5                                      7    Cl     Cl     Me    Me   Me         Oil                                   8    Br     H      Me    Me   Me         140-142                               9    Cl     H      Me    together are  130-131                                                          (CH.sub.2).sub.4                                      10   Cl     H      Me    together are  89-90                                                            (CH.sub.2 ).sub.6                                     11   Cl     H      Me    together are  165-175                                                          CHCH(CH.sub.2).sub.3                                  12   Cl     H      Me    Me   CH.sub.2 COOEt                                                                            157-158                               13   Cl     H      Me    Me   CH.sub.2 COOMe                                                                            139-140                               14   Cl     H      Me    Me   Pr.sup.i   90-92                                 15   Cl     H      Me    together are  112-115                                                           ##STR10##                                            16   Cl     H      Me    Me   Bu.sup.i   Oil                                   17   Cl     H      CF.sub.3                                                                             together are  105.5-106.5                                                      (CH.sub.2).sub.6                                      18   Cl     H      Me    Me   CH.sub.2 CH.sub.2 Ph                                                                      Oil                                   19   Cl     H      Me    together are  Oil                                                               ##STR11##                                            20   Cl     H      Me    Me   CH.sub.2 CHCH.sub.2                                                                       Oil                                   21   Cl     H      Me    Me   CH.sub.2 OPh                                                                              Oil                                   22   Cl     H      Me    together are  Oil                                                               ##STR12##                                            23   Cl     H      Me    Me   CH.sub.2 F 111.5-112.5                           24   Cl     H      CF.sub.3                                                                             together are  Oil                                                               ##STR13##                                            25   Cl     H      Me    Me   CH.sub.2 NMe.sub.2                                                                        Oil                                   26   Cl     H      Me    together are  Oil                                                               ##STR14##                                            27   Cl     H      Me    together are  120-121                                                           ##STR15##                                            28   Cl     H      Me    together are  171-172                                                          (CH.sub.2).sub.3                                      29   Cl     H      Me    Me   Bu.sup.t   72-73                                 30   Cl     H      Me    Me                                                                                   ##STR16##  99-102                               31   Cl     H      Me                                                                                    ##STR17##                                                                           ##STR18## 158-160                               32   Cl     H      CF.sub.3                                                                             Me                                                                                   ##STR19## Oil                                   33   Cl     H      Me    Me   CH.sub.2 Ph                                                                               Oil                                   34   Cl     H      Me    Me                                                                                   ##STR20## 88-98                                 35   Cl     H      Me    Me                                                                                   ##STR21## Oil                                   36   Cl     H      Me    Me                                                                                   ##STR22## Oil                                   37   Cl     H      Me    Me                                                                                   ##STR23## Oil                                   38   Cl     H      Me    H                                                                                    ##STR24## 114-115                               39   Cl     H      CF.sub.3                                                                             Me                                                                                   ##STR25## Oil                                   40   CF.sub.3                                                                              H      CF.sub.3                                                                             Me   Me         60-62                                 41   Cl     H      CF.sub.3                                                                             together are  Oil                                                              CHCH(CH.sub.2).sub.3                                  42   Cl     H      Me.sub.2 N                                                                           Me   Me         Oil                                   43   Cl     H      Me    Me   CH.sub.2 CN                                                                               134-135                               ______________________________________                                    

The intermediates in Examples 5, 7, 8, 17, 24, 32, 39, 40, 41 and 42 had melting points as follows:

    ______________________________________                                         Ex. No.  Type A      Type B      Type C                                        ______________________________________                                         5,17,24,32,                                                                    39, and 41                                                                              179-181     57-60       84-99                                          7       134-135     119-120     Oil                                            8       187.5-191     135-136.5 110-113                                       40       136-138     42-44         123-124.5                                   42       179-181     81.5-82.5     110-116.5                                   ______________________________________                                    

EXAMPLES 44-57A

Pyridinium chloride (0.05 g.) was added to a solution of C from Example 1 (20 g.) in triethyl orthoformate (50 ml.) and the mixture heated on a steam bath for 8 hours. Ethanol which formed was distilled off as it was produced. The mixture was treated with charcoal, filtered and evaporated under reduced pressure to give an oil which on trituration with ethanol solidified and the resulting product was recrystallised from ethanol to give ethyl N-(4-chlorophenyl-4-methylsulphonyloxyphenylmethylene)formohydrazonate, m.p. 104°-107° C.

In a similar manner the appropriate intermediate C was reacted with various esters or acetals to give products as follows.

                                      TABLE II                                     __________________________________________________________________________      ##STR26##                                                                          Ester or                                                                  Ex. No.                                                                             acetate.   R.sup.3                                                                            R.sup.5                                                                           R.sup.6   m.p. (°C.)                             __________________________________________________________________________     45   (EtO).sub.3 CMe                                                                           Me  Me OEt       109-112                                       46   (PrO).sub.3 CH                                                                            Me  H  OPr       128-130                                       47   (EtO).sub.3 CEt.sup.1                                                                     Me  Et OEt       94-99                                         48   (MeO).sub.3 CBu.sup.1                                                                     Me  Bu OMe       94-95                                         49   (EtO).sub.3 CH.sup.2                                                                      CF.sub.3                                                                           H  OEt       58-69                                         50   (EtO).sub.3 CEt.sup.1                                                                     CF.sub.3                                                                           Et OEt       Oil                                           51   (Pr.sup.i O).sub.3 CH.sup.2                                                               CF.sub.3                                                                           H  OPr.sup.1 Oil                                           52   (EtO).sub.3 CMe                                                                           CF.sub.3                                                                           Me OEt       Oil                                           53   (EtO).sub.3 CMe                                                                           Me.sub.2 N                                                                         Me OEt       104-105                                       54   (CH.sub.2CHCH.sub.2 O).sub.3 CH                                                           CF.sub.3                                                                           H  CH.sub.2CHCH.sub.2 O                                                                     Oil                                           55   (PrO).sub.3 CH                                                                            CF.sub.3                                                                           H  OPr       Oil                                           56   Me.sub.2 NCH(OEt).sub.2.sup.1                                                             Me  H  NMe.sub.2 162- 170                                      57   Me.sub.2 NCH(OEt).sub.2.sup.1                                                             CF.sub.3                                                                           H  NMe.sub.2 133                                           __________________________________________________________________________      .sup.1 No pyridinium hydrochloride used                                        .sup.2 Acetic acid replaced the pyridinium hydrochloride.                

EXAMPLES 57B AND 57C

A solution of product of Example 47 (10 g.) in n-butylamine (25 ml.) was refluxed for 24 hours. After treatment with charcoal, excess n-butylamine was distilled and the product subjected to vaccum to give N"-butyl-N-(4'-chlorophenyl-4-methylsulphonyloxyphenylmethylene)propioamidrazone, as a clear oily liquid.

In a similar manner but replacing the n-butylamine with cyclopropylamine and heating in a sealed tube, there was obtained N-(4'-chlorophenyl-4-methylsulphonyloxyphenylmethylene-N"-cyclopropylpropioamidrazone, as an oil.

EXAMPLE 57D

A solution of concentrated sulphuric acid (0.05 ml) in trimethyl orthoformate (5 ml) was added to a solution of intermediate C from Example 5 (10 g) in trimethyl orthoformate (50 ml) and the mixture heated for 10 hours on a steam bath. Methanol was allowed to distil as it was formed and the mixture then boiled for 3 hours during which time further methanol was distilled through a column. Excess trimethyl orthoformate was then distilled and the residue was extracted with light petroleum (b.p. 60°-80° C.) and the extract worked up in conventional manner to give methyl-N-(4-chlorophenyl-4-trifluoromethylsulfphenyloxyphenylmethylene)formohydrazonate, obtained as an oil.

In a similar manner to Example 44, but omitting the pyridinium hydrochloride, methyl N-2,4-dimethylphenylformimidate gave 4-chloro-4'-methylsulphonyloxybenzophenone 2,4-dimethylphenyliminomethylhydrazone, as a glass like solid (Example 58) and ethyl N-4-chloro-2-methylphenylformimidate gave 4-chloro-4'-methylsulphonyloxybenzophenone 4-chloro-2-methylphenyliminomethylhydrazone m.p. 60->100° C. (Example 59).

EXAMPLES 60-65

In a similar manner to that described in Example 1, the various 4-substituted 4'-hydroxybenzophenones (Intermediates A) were formed and converted to the corresponding 4'-methylsulphonylbenzophenones (Intermediates B). These (6 g.) were then heated under reflux with ethyl carbazate (4.3 g.) in ethanol (86 ml.) for 24 hours. The mixtures were then evaporated under reduced pressure and dissolved in dichloromethane. These solutions were washed with water, aqueous sodium hydroxide, water, dilute hydrochloric acid and evaporated under reduced pressure to give the products shown in the following table.

                  TABLE III                                                        ______________________________________                                          ##STR27##                                                                                            m.p. of m.p. of m.p. of                                 Ex.                    product interme-                                                                               interme-                                No.  R          R.sup.1                                                                               (°C.)                                                                           diate A diate B                                 ______________________________________                                         60   OPh        H      Resin   140     144-146                                 61   CHCH.sub.2 H      Resin   97-99   97-98                                   62   CH Ph      H      Resin   134.5-135.5                                                                            85.5-87                                 63   Ph         H      Oil     176.5-180                                                                              139-140                                 64   CN         H        105-107.5                                                                             180-184*                                                                              119-120                                 65   Cl         CN     155-156  120-121*                                                                              120-121                                 ______________________________________                                          *Prepared from corresponding bromo compound by reaction with cuprous           cyanide in dimethyl formamide and extraction with dichloromethane.       

EXAMPLES 66-68

4-Amino-4'-chlorobenzophenone (4 g.) was heated under reflux with a mixture of pyridine (15 ml.) and methanesulphonyl chloride (10 g.) for 30 mins. The mixture was then poured into a mixture of ice and hydrochloric acid and then filtered to give 4-chloro-4'-methylsulphonylaminobenzophenone m.p. 198°-200° C. A mixture of this product (2.4 g.) ethyl carbazate (2 g.) and a trace amount of pyridine hydrochloride in ethanol (50 ml.) was heated under reflux for 24 hours. The mixture was then cooled to 0° C. and filtered to give 4-chloro-4'-methylsulphonylaminobenzophenone ethoxycarbonyl hydrazone, m.p. 198°-200° C.

In a similar manner there was also obtained 4-chloro-4'-phenylsulphonylaminobenzophenone m.p. 183°-184° C. which gave 4-chloro-4'-phenylsulphonylaminobenzophenone ethylcarbonylhydrazone m.p. 238°-240° C. (Example 67); and 4-chloro-4'-ethoxycarbonylaminobenzophenone, m.p. 171°-172° C. (from ethyl chloroformate) which gave 4-chloro-4'-ethoxycarbonylaminobenzophenone ethoxycarbonylhydrazone, m.p. 228°-229° C. (Example 68).

EXAMPLES 69-73

A mixture of 4-hydroxyacetophenone (7.8 g.) methyl carbazate (5.5 g.), ethanol (100 ml.) and glacial acetic acid (1.5 ml.) was heated under reflux for 24 hours. The mixture was cooled, filtered and the product dried to give 4-hydroxyacetophenone methoxycarbonylhydrazone, m.p. 209°-212° C. (Intermediate F). A solution of trifluoromethanesulphonyl chloride (8.58 g.) in tetrahydrofuran (20 ml.) was added dropwise with stirring to a solution of F (9.62 g.) in triethylamine (11.5 ml.) cooled to 0° C. over 25 minutes. The mixture was stirred overnight at room temperature. The mixture was poured into water and filtered and the product recrystallised from industrial methylated spirits to give 4-trifluoromethylsulphonyloxyacetophenone methoxycarbonylhydrazone, m.p. 135°-137° C.

In a similar manner starting from the appropriate 4-hydroxyacetophenone or 4-hydroxybenzaldehyde type F intermediates were formed using ethyl carbazate instead of methyl carbazate for which the corresponding 4-trifluoromethylsulphonyl compounds were formed as shown in Table IV.

                  TABLE IV                                                         ______________________________________                                          ##STR28##                                                                                                m.p. of type F intermediate                         Ex. No. R.sup.14                                                                               m.p. (°C.)                                                                         (°C.)                                        ______________________________________                                         70      Et      106-110    144-148                                             71      Me      131-133    177-179                                             72      H       124--127   214-218                                             73                                                                                      ##STR29##                                                                             91-93      162-164                                             ______________________________________                                    

EXAMPLES 74-77

A solution of A from Example 1 (92.8 g.) ethyl carbazate (100 g.) and glacial acetic acid (100 ml.) in ethanol (1 liter) was heated under reflux, with stirring, for 48 hours. Evaporation of solvent under reduced pressure gave a slurry and the solid was separated from the liquors by filtration. This solid was washed with a little cold industrial methylated spirit and then dried in vacuo at 50° C.

The liquors were evaporated again under reduced pressure and the resulting oil was extracted with chloroform and the extract washed with aqueous sodium carbonate and then water. The extract was dried over magnesium sulphate and evaporated under reduced pressure to give a second batch of solid.

The combined solid material was recrystallised from industrial methylated spirits to give 4-chloro-4'-hydroxybenzophenone ethoxycarbonylhydrazone, mp. 185°-187° C. (E). To a solution of (E) (19.2 g.) in dry pyridine (150 ml) cooled to 0° C. was added cooled sulphuryl chloride fluoride (10 g.) over 30 minutes. The mixture was stirred at 0° C. for 3 hours and then for 1 hour at 40° C. The mixture was poured into a mixture of ice and dilute hydrochloric acid and then extracted with ether. The extract was dried and evaporated to dryness to give a glass-like product which was purified on an alumina column to give 4'-chloro-4'-fluorosulphonyloxybenzophenone ethoxycarbonylhydrazone, obtained as a glass, whose structure was confirmed by mass spectrometry.

In a similar manner starting from E and using the appropriate chloride there was obtained 4-chloro-4'-(4-nitrophenylsulphonyloxy)benzophenone ethoxycarbonyl hydrazone, m.p. 141°-7° C. (Example 75); 4-chloro-4'-[3,5-di(trifluoromethyl)phenylsulphonyloxy]benzophenone ethoxycarbonylhydrazone, m.p. 134°-8° (Example 76); and 4-chloro-4'-(2,2,2-trifluoroethoxycarbonyloxy)benzophenone ethoxycarbonylhydrazone, m.p. 115°-117° C. (Example 77). In the case of Example 75 the pyridine was replaced by a mixture of triethylamine and tetrahydrofuran and the product obtained by recrystallisation of the evaporated reaction mixture from n-butanol. In the case of Example 76 the pyridine was replaced by a mixture of triethylamine and 4-dimethylaminopyridine and the product obtained by recrystallisation of the evaporated reaction mass from isopropanol.

EXAMPLES 78-93

In a similar manner to that described in Example 1 intermediate A or related 4'-substituted-4-hydroxybenzophenones were reacted with various chloro compounds in a similar manner to that described in Example 1 to give type B intermediate. These were then treated with hydrazine or hydrazine derivatives in a similar manner to that described in Example 60 to give the following products.

                                      TABLE V                                      __________________________________________________________________________      ##STR30##                                                                                                  mp. of mp of B                                    Ex. No.                                                                             R           R.sup.1                                                                           R.sup.2                                                                               R.sup.4                                                                          product(°C.)                                                                   (°C.)                               __________________________________________________________________________     78                                                                                   ##STR31##  Cl COOEt  H 100-116                                                                               101-102                                    79                                                                                   ##STR32##  Cl H      H 87.5   101-102                                    80                                                                                   ##STR33##  Cl COOEt  H 154-160                                                                               132-134                                    81                                                                                   ##STR34##  Cl COOEt  H 170-180                                                                               112-114                                    82   Cl.sub.2 CHCF.sub.2 O                                                                      Cl COOEt  H 105-118                                                                               78.5-81                                    83   Cl.sub.2 CHCF.sub.2 O                                                                      Cl H      H Oil    78.5-81                                    84   CF.sub.2 HO Cl COOEt  H 89-91  85-86.5                                    85   CF.sub.2 HO Cl CO.sub.2 CH.sub.2 CCl.sub.3                                                           H 100-114                                                                               85-86.5                                    86   Cl.sub.2 CHCF.sub.2 O                                                                      CF.sub.3                                                                          COOEt  H  96-136                                                                               74-76                                      87                                                                                   ##STR35##  Cl COOEt  H 131-149                                                                               106-108                                    88                                                                                   ##STR36##  Cl COOEt  H 155-162                                                                               134-135.5                                  89   Cl.sub.2 CHCF.sub.2 O                                                                      Cl COO(CH.sub.2).sub.2                                                                     121-129                                                                               78.5-81                                    90   MeSO.sub.2 O                                                                               Cl                                                                                 ##STR37##                                                                            H 192-193                                                                               120-121                                    91   Cl.sub.2 CHCF.sub.2 O                                                                      F  COOEt  H 117-132                                                                               55-57                                      92   Cl.sub.2 CHCF.sub.2 O                                                                      MeO                                                                               COOEt  H 115-123                                                                               96-98                                      93   CF.sub.2 HO Cl H      H Oil    85- 86.5                                   __________________________________________________________________________

The hydrazine derivatives used were as follows:

ethyl carbazate--Examples 78,80,81,82,86,87,88,91 and 92

hydrazine hydrate--Examples 79,83,84 and 93

2,2,2-trichloroethyl carbazate--Example 85

3-amino-2-oxazolidine--Example 89

4-methylthiazol-2-yl hydrazine--Example 90

The chloro compounds used were as follows:

p-chlorophenyl chlorosulphate--Examples 78 and 79

N-methylsulphamoyl chloride--Example 80

N-ethylsulphamoyl chloride--Example 81

1,1-difluoro-1,2,2-trichloroethane--Example 82,83,86,89,91 and 92

chlorodifluoromethane--Examples 84, 85 and 93

methanesulphonyl chloride--Example 90

In Examples 87 and 88 intermediate B was prepared by a Friedel-Crafts reaction between 4-chlorobenzoyl chloride and the appropriate alkylthiobenzene to give the benzophenone followed by oxidation with hydrogen peroxide.

In Examples 91-93 the 4'-hydroxybenzophenone was converted to its sodium derivative by reaction with sodium hydroxide before treatment with the chloro compound.

EXAMPLE 94

In a similar manner to Example 78 4-hydroxyacetophenone was converted to 4-(2,2-dichloro-1,1-difluoroethoxy) acetophenone, obtained as a liquid which on treatment with ethyl carbazate gave the corresponding ethoxycarbonylhydrazone m.p. 166°-168° C.

EXAMPLE 95

Methanesulphonyl chloride (3.78 g.) in dry ether (15 ml.) was added dropwise over 30 minutes to intermediate C from Example 1 (9.75 g.) in dry pyridine (20 ml.). The mixture was kept at below -5° C. and maintained at this temperature with stirring for a further 30 minutes and then stirred overnight at room temperature. It was then poured into water and extracted with chloroform. The extract was washed with hydrochloric acid (5 N) and water, dried and evaporated to dryness under reduced pressure. The product was recrystallised from industrial methylated spirits to give 4-chloro-4'-methylsulphonyloxybenzophenonemethylsulphonylhydrazone, m.p. 160°-165°.

In a similar manner starting from the appropriate hydrazone and using the appropriate sulphonyl chloride the following compounds were also obtained.

                  TABLE VI                                                         ______________________________________                                          ##STR38##                                                                     Ex. No.  R.sup.3  R.sup.13       m.p. (°C.)                             ______________________________________                                         96       Me       Ph               193-194.5                                   97       Me       Pr             140-143                                       98       Me                                                                                       ##STR39##       195-200.5                                   99       Me       CH.sub.2 Cl    127-130                                       100*     CF.sub.3 Me             131-144                                       101      Me       Et             112-120                                       102*     CF.sub.3 Ph             135.5-138.5                                   103      Me                                                                                       ##STR40##     198-200                                       104      Me                                                                                       ##STR41##     176-177                                       105      Me                                                                                       ##STR42##     179-181                                       106*     CF.sub.3                                                                                 ##STR43##     108.5-115                                     ______________________________________                                          *Starting material was Intermediate C from Example 5.                    

EXAMPLES 107-109

To the product of Example 83 (6.1 g) in pyridine (20 ml) was added dropwise with stirring a solution of benzoyl chloride (2.47 g) in ether (15 ml.) and stirring continued overnight. Water was added and the mixture worked up in conventional manner to give 4-chloro-4'-(2,2-dichloro-1,1-difluoroethoxy)benzophenone benzoylhydrazone, m.p. 121°-122° C.

In a similar manner but replacing the benzoyl chloride with 2,2,2-trichloroethylchloroformate there was obtained 4-chloro-4'-(2,2-dichloro-1,1-difluoroethoxy)benzophenone 2,2,2-trichloroethoxycarbonylhydrazone, m.p. 97°-103° C. (Example 108).

In a similar manner the product of Example 93 and butyryl chloride gave 4-chloro-4'-difluoromethoxybenzophenone butyrylhydrazone m.p. 114°-125° C. (Example 109).

EXAMPLE 10

A mixture of the product of Example 47 (10 g) and ammonium chloride (1.32 g) in methanol (150 ml) was refluxed for 20 hours. The mixture was cooled and filtered and the precipitate recrystallised from ethanol to give 1,7-di(4-chlorophenyl)-4-ethyl-1,7-di-(4-methylsulphonyloxyphenyl)-2,3,5,6-tetraazahepta-1,3,6-triene, m.p. 184°-5° C.

EXAMPLE 111

A solution of intermediate B from Example 1 in ethanol was refluxed with a mixture of hydrazine hydrate and glacial acetic acid and the mixture then worked up in conventional manner to give 4-chloro-4'-methylsulphonyloxybenzophenone hydrazone. This was then converted to the corresponding ethoxycarbonyl hydrazone by reaction with acetyl chloride in the presence of pyridine. The product was separated into its geometric isomers by high pressure liquid phase chromatography. The E-isomer (2 g.) in dry ether was refluxed for 100 hours with a mixture of allyl bromide (1.21 g.) and 50% sodium hydroxide (0.48 g.). Ether was added and the mixture filtered and evaporated. The residue was extracted with light petroleum (b.p. 62°-68° C.) and evaporated to give (E)-4-chloro-4'-methylsulphonyloxybenzophenone N-allyl-N-ethoxycarbonylhydrazone, obtained as an oil.

EXAMPLES 112-113

A mixture of E from Example 74 (5 g.) potassium carbonate (4.3 g.) and diethylchlorophosphate (4.5 ml.) in acetone (50 ml.) was heated under reflux for 24 hours. The mixture was then poured into water (150 ml.) and extracted with dichloromethane. The extract was dried, evaporated to dryness and the residue distilled under reduced pressure to give 4-chloro-4'-(diethoxyphosphinyloxy)benzophenone ethoxycarbonylhydrazone, obtained as an oil.

In a similar manner using diethylchloromonothiophosphate, there was obtained 4-chloro-4'(diethoxyphosphinothioyloxy) benzophenone ethoxycarbonylhydrazone m.p. 106°-106.5° C.

EXAMPLE 114

N-(2,4-dimethylphenyl)-N'-methylformamidine (2.9 g.) was added to a warm solution of the product of Example 44 (6.7 g.) in isopropanol (30 ml.). The mixture was heated on a steam bath for 15 mins and then evaporated in vacuo. The residual oil was heated on a steam bath for a further 24 hours. Isopropanol was added and oil which separated on cooling was collected and evaporated in vacuo to give 4-chlorophenyl-(4-methylsulphonyloxyphenyl)methylene N-(2,4-dimethylphenyliminomethyl)-N-methylformamidehydrazone, as a glass-like solid.

EXAMPLE 115

A solution of C from Example 1 (10 g) in pyridine (20 ml) was mixed with diethylchlorophosphate (4.9 ml) and a trace of dimethylaminopyridine and the mixture stirred for 24 hours at room temperature. It was then extracted with dichloromethane and the extract evaporated to dryness. The oil which remained was subjected to thin layer chromatography to give 4-chloro-4'-methylsulphonyloxybenzophenone diethoxyphosphinylhydrazone, m.p. 90°-91° C.

EXAMPLE 116

Propionic acid (3.9 ml) and trifluoroacetic anhydride (5.6 ml) were heated together at 60° C. for 5 minutes. To this was added E (9.56 g) from Example 74, portionwise, and the mixture heated at 60° C. for 40 minutes and then allowed to cool for one hour. The mixture was then poured into aqueous sodium bicarbonate and extracted with chloroform. The extract was washed with aqueous sodium bicarbonate and water, dried and evaporated to dryness under reduced pressure. The residue was triturated with light petroleum (b.p. 62°-68° C.) to give a solid which on recrystallisation from methylene dichloride/light petroleum (b.p. 40°-60° C.) gave 4-chloro-4'-propionyloxybenzophenone ethoxycarbonylhydrazone m.p. 120°-146°.

EXAMPLE 117

The following types of compositions were formulated as below:

    ______________________________________                                                          w/v (%)                                                       ______________________________________                                         Water dispersible concentrate                                                  Product of Example 1                                                                              8                                                           Sopraphor S25.sup.1                                                                               3                                                           Sopraphor S70.sup.2                                                                               2                                                           N-Methylpyrrolidone                                                                               to 100                                                      Emulsifiable concentrate                                                       Product of Example 45                                                                             12.5                                                        Atlox 4851 B.sup.3 1.5                                                         Atlox 4855 B.sup.3 3.5                                                         Esso 200.sup.4     to 100                                                      Emulsifiable concentrate                                                       Product of Example 49                                                                             30                                                          Atlox 4851B.sup.3  5                                                           Atlox 4855B.sup.3  5                                                           Xylene             to 100                                                      Seed Dressing                                                                  Product of Example 49                                                                             10                                                          Dowanol DPM.sup.5  to 100                                                      ______________________________________                                          .sup.1 Ethoxylated polyarylphenol                                              .sup.2 Calcium alkylarylsulphonate                                             .sup.3 Blends of calcium dodecylbenzenesulphonate and a triglyceride           ethoxylate.                                                                    .sup.4 High boiling aromatic solvent                                           .sup.5 Dipropylene glycol methyl ether                                   

EXAMPLE 118

This Example illustrates the activity of compounds of the invention against larvae of the diamond back moth (Plutella xylostella).

Ten larvae were placed in a small container together with a square inch of cabbage which had been dipped in the test solution and allowed to dry. After twenty-four hours, untreated cabbage was added for food and, after a further twenty-four hours, an assessment was made of the mortality of the larvae.

Two replicates were carried out for each test compound and test solutions of varying concentrations employed so that an LD₅₀ value could be calculated.

The compounds of Examples 1 to 52, 56, 57A, B and C, 58-82, 84-89, 90, 94-107 and 110-116 had an LD₅₀ of less than 5000 ppm. 

We claim:
 1. Compounds of formula I ##STR44## in which Q is p-halophenyl or p-trifluoromethylphenyl and R is R³ SO₂ O where R³ is alkyl or haloalkyl and R² and R⁴ together form the group ═CR⁵ R⁶, where R⁵ and R⁶ may be the same or different and are hydrogen, alkyl, alkenyl, alkoxy, alkenyloxy groups (which groups, other than hydrogen, may be optionally substituted by halo, phenyl, phenoxy, cyano, alkylamino or alkoxycarbonyl) monoalkylamino, dialkylamino, monocycloalkyloamino, cycloalkyl (optionally substituted by C₁₋₄ alkyl), phenyl, phenoxy, pyridyl or thienyl or R⁵ and R⁶ together with the carbon to which they are attached form a 4-7 carbon membered ring, which may optionally be unsaturated and may optionally be substituted by alkyl or by two substituents which form a fused 6-membered ring.
 2. Compounds according to claim 1 in which Q is 4-chlorophenyl.
 3. Compounds according to claims 1 or 2 in which R is methylsulphonyloxy or trifluoromethylsulphonyloxy.
 4. Compounds according to claim 1 in which R is trifluoromethylsulphonyloxy or methanesulphonyloxy, Q is 4-chlorophenyl and R² and R⁴ form the group ═CR⁵ R⁶ where one of R⁵ and R⁶ is hydrogen or C₁₋₄ alkyl and the other is C₁₋₄ alkoxy.
 5. A compound according to claim 1 which is ethyl N-(4-chlorophenyl-4-trifluoromethylsulphonyloxyphenylmethylene)formohydrazonate.
 6. A compound according to claim 1 which is ethyl N-(4-chlorophenyl-4-trifluoromethylsulphonylxyphenylmethylene)acetohydrazonate.
 7. A compound according to claim 1 which is methyl N-(4-chlorophenyl-4-trifluoromethylsulphonyloxyphenylmethylene)formohydrazonate.
 8. An insecticidal composition comprising an effective amount of a compound according to claim 1 and an inert diluent or carrier.
 9. A composition according to claim 8 in which the compound is a compound wherein R is trifluoromethylsulphonyloxy or methanesulphonyloxy, Q is 4-chlorophenyl and R² and R⁴ form the group ═CR⁵ R⁶ where one of R⁵ and R⁶ is hydrogen or C₁₋₄ alkyl and the other is C₁₋₄ alkoxy.
 10. A method of combating insects which comprise applying an effective amount of a compound according to claim 1 to the locus of the insects.
 11. A method according to claim 10 wherein the locus is a plant or an animal. 